WO2018003764A1 - Pneumatic tire - Google Patents

Pneumatic tire Download PDF

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Publication number
WO2018003764A1
WO2018003764A1 PCT/JP2017/023479 JP2017023479W WO2018003764A1 WO 2018003764 A1 WO2018003764 A1 WO 2018003764A1 JP 2017023479 W JP2017023479 W JP 2017023479W WO 2018003764 A1 WO2018003764 A1 WO 2018003764A1
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WO
WIPO (PCT)
Prior art keywords
rubber
mass
parts
inner liner
rubber composition
Prior art date
Application number
PCT/JP2017/023479
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French (fr)
Japanese (ja)
Inventor
克典 清水
強 野間口
Original Assignee
横浜ゴム株式会社
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Publication date
Application filed by 横浜ゴム株式会社 filed Critical 横浜ゴム株式会社
Priority to KR1020187035909A priority Critical patent/KR102273158B1/en
Priority to RU2019102601A priority patent/RU2699673C1/en
Priority to EP17820118.2A priority patent/EP3480250B1/en
Priority to CN201780041008.4A priority patent/CN109415547A/en
Priority to US16/310,806 priority patent/US11766891B2/en
Publication of WO2018003764A1 publication Critical patent/WO2018003764A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C5/00—Inflatable pneumatic tyres or inner tubes
    • B60C5/12—Inflatable pneumatic tyres or inner tubes without separate inflatable inserts, e.g. tubeless tyres with transverse section open to the rim
    • B60C5/14—Inflatable pneumatic tyres or inner tubes without separate inflatable inserts, e.g. tubeless tyres with transverse section open to the rim with impervious liner or coating on the inner wall of the tyre
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • B60C1/0008—Compositions of the inner liner
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L15/00—Compositions of rubber derivatives
    • C08L15/02—Rubber derivatives containing halogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • C08L23/28—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with halogens or compounds containing halogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • C08L23/28—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with halogens or compounds containing halogen
    • C08L23/283—Halogenated homo- or copolymers of iso-olefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C5/00—Inflatable pneumatic tyres or inner tubes
    • B60C5/12—Inflatable pneumatic tyres or inner tubes without separate inflatable inserts, e.g. tubeless tyres with transverse section open to the rim
    • B60C5/14—Inflatable pneumatic tyres or inner tubes without separate inflatable inserts, e.g. tubeless tyres with transverse section open to the rim with impervious liner or coating on the inner wall of the tyre
    • B60C2005/145—Inflatable pneumatic tyres or inner tubes without separate inflatable inserts, e.g. tubeless tyres with transverse section open to the rim with impervious liner or coating on the inner wall of the tyre made of laminated layers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/006—Additives being defined by their surface area
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

Definitions

  • the present invention relates to a pneumatic tire in which handling stability and crack growth resistance in a low temperature environment are improved.
  • ⁇ Inner liners for pneumatic tires are required to have excellent heat permeability, low heat buildup, high hardness, and excellent crack growth resistance. Low heat generation, high hardness, and crack growth resistance are important characteristics that affect the low fuel consumption performance, steering stability and durability of pneumatic tires.
  • Patent Document 1 discloses at least one weak reinforcement selected from the group consisting of recycled butyl rubber, halogenated butyl rubber, bituminous coal pulverized material, talc, mica, and hard clay in order to improve handling stability, fuel efficiency, and air barrier properties.
  • a rubber composition for an inner liner is described in which a functional filler, carbon black having a nitrogen adsorption specific surface area of 20 to 35 m 2 / g, zinc oxide, and a mixed resin are blended.
  • a functional filler carbon black having a nitrogen adsorption specific surface area of 20 to 35 m 2 / g, zinc oxide, and a mixed resin are blended.
  • An object of the present invention is to provide a pneumatic tire in which the handling stability and the crack growth resistance in a low temperature environment are improved to the conventional level or more.
  • the pneumatic tire of the present invention that achieves the above object is a pneumatic tire having an inner liner and a tie rubber, wherein the rubber composition for the inner liner constituting the inner liner contains 50 to 100 parts by mass of a halogenated butyl rubber. 100 parts by mass of diene rubber, 25 to 75 parts by mass of carbon black having a nitrogen adsorption specific surface area of 25 to 95 m 2 / g, 1 to 13 parts by mass of resin, and 0.1 to 1.8 parts by mass of zinc oxide
  • the dynamic storage elastic modulus at ⁇ 45 ° C. is 600 MPa or less.
  • a diene rubber containing 50 to 100 parts by mass of a halogenated butyl rubber, 25 to 75 parts by mass of specific carbon black, 1 to 13 parts by mass of resin, and 0.1% of zinc oxide.
  • the dynamic storage elastic modulus at ⁇ 45 ° C. of the rubber composition for the inner liner compounded with 1 to 1.8 parts by mass is reduced to 600 MPa or less, so that the handling stability and the crack growth resistance in a low temperature environment are improved to the conventional level or more. Can be made.
  • the number of repeated repeated deformations in the constant strain fatigue test with a strain rate of 120% and a frequency of 6.67 Hz of the rubber composition for the inner liner is preferably 800,000 times or more.
  • FIG. 1 is a cross-sectional view in the meridian direction showing an example of an embodiment of a pneumatic tire of the present invention.
  • the pneumatic tire has a tread portion 1, a side portion 2, and a bead portion 3, a carcass layer 4 is mounted between the left and right bead portions 3, 3, and both end portions thereof are around the bead core 5.
  • a belt layer 6 is disposed outside the carcass layer 4 in the tire tread portion 1 in the tire radial direction, and a tread rubber 9 is disposed outside the belt layer 6.
  • a tie rubber 7 is disposed on the inner side of the carcass layer 4 in the tire radial direction, and an inner liner 8 is further disposed on the inner side.
  • the inner liner 8 is a layer molded using a rubber composition for an inner liner
  • the tie rubber 7 is a layer molded using a rubber composition for a tie rubber.
  • the rubber component of the rubber composition for the inner liner is a diene rubber and includes a halogenated butyl rubber.
  • the content of the halogenated butyl rubber is 50 to 100% by mass, preferably 60 to 80% by mass, in 100% by mass of the diene rubber. By setting the content of halogenated butyl rubber to 50% by mass or more, air permeation preventing performance can be ensured.
  • Examples of the halogenated butyl rubber include brominated butyl rubber and chlorinated butyl rubber.
  • the diene rubber can contain other diene rubbers other than the halogenated butyl rubber.
  • diene rubbers include butyl rubber, natural rubber, isoprene rubber, butadiene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, and the like, and they can be used alone or as a blend.
  • the rubber composition for the inner liner increases the rubber hardness and the crack growth resistance by adding carbon black.
  • the compounding amount of carbon black is 25 to 75 parts by mass, preferably 30 to 70 parts by mass with respect to 100 parts by mass of the diene rubber.
  • the blending amount of carbon black is less than 25 parts by mass, the rubber hardness of the rubber composition cannot be sufficiently obtained, and the steering stability is lowered.
  • the blending amount of the carbon black exceeds 75 parts by mass, the dynamic storage elastic modulus at ⁇ 45 ° C. increases and the crack growth resistance decreases.
  • the nitrogen adsorption specific surface area N 2 SA is 25 ⁇ 95m 2 / g, preferably from 30 ⁇ 55m 2 / g.
  • N 2 SA is less than 25 m 2 / g, mechanical properties such as rubber hardness and dynamic elastic modulus of the rubber composition for the inner liner are lowered, and there is a fear that the crack growth resistance is insufficient.
  • N 2 SA exceeds 95 m 2 / g, rolling resistance increases. Moreover, crack growth resistance falls.
  • Such carbon black can be appropriately selected and used from HAF class to GPF class.
  • the N 2 SA of carbon black shall be measured according to JIS K6217-2.
  • the rubber composition for the inner liner includes a resin.
  • the resin include petroleum resins and / or aromatic resins.
  • the compounding amount of the resin is 1 to 13 parts by mass, preferably 3 to 10 parts by mass with respect to 100 parts by mass of the diene rubber.
  • the blending amount of the resin is less than 1 part by mass, the rubber hardness cannot be sufficiently improved.
  • the amount of the resin exceeds 13 parts by mass, the dynamic storage elastic modulus at ⁇ 45 ° C. increases and crack growth resistance decreases. Moreover, there exists a possibility that the air permeation prevention performance may fall.
  • Petroleum resins are aromatic hydrocarbon resins or saturated or unsaturated aliphatic hydrocarbon resins produced by polymerizing components obtained by subjecting crude oil to distillation, decomposition, reforming, and the like.
  • Examples of petroleum resins include C5 petroleum resins (aliphatic petroleum resins obtained by polymerizing fractions such as isoprene, 1,3-pentadiene, cyclopentadiene, methylbutene, and pentene), C9 petroleum resins ( ⁇ -methylstyrene, o -Aromatic petroleum resin obtained by polymerizing a fraction such as vinyltoluene, m-vinyltoluene, p-vinyltoluene), C5C9 copolymerized petroleum resin, and the like.
  • the aromatic resin is a polymer having at least one segment composed of an aromatic hydrocarbon, such as coumarone resin, phenol resin, alkylphenol resin, terpene resin, rosin resin, novolac resin, resole resin, etc. Can give. These resins can be used alone or as a blend.
  • the C9 petroleum resin described above is an aromatic hydrocarbon resin, but is classified as a petroleum resin in this specification.
  • the rubber composition for the inner liner is blended with 0.1 to 1.8 parts by mass, preferably 0.2 to 1.6 parts by mass of zinc oxide with respect to 100 parts by mass of the diene rubber.
  • zinc oxide By blending zinc oxide, rubber hardness can be secured and steering stability can be improved.
  • the blending amount of zinc oxide is less than 0.1 parts by mass, the rubber hardness is insufficient.
  • the blending amount of zinc oxide exceeds 1.8 parts by mass, the dynamic storage elastic modulus at ⁇ 45 ° C. is increased and the crack growth resistance is lowered. In addition, steering stability is reduced.
  • the dynamic storage elastic modulus at ⁇ 45 ° C. of the rubber composition for the inner liner is 600 MPa or less, preferably 410 to 590 MPa.
  • the dynamic storage elastic modulus at ⁇ 45 ° C. is measured under conditions of an initial strain of 10%, a dynamic strain of ⁇ 2%, a frequency of 20 Hz, and a temperature of ⁇ 45 ° C.
  • the number of repeated repeated deformations in the constant strain fatigue test of the rubber composition for the inner liner is preferably 800,000 times or more, more preferably 810,000 to 990,000 times.
  • the constant strain fatigue test is based on tensile fatigue characteristics described in JIS-K6270, using a dumbbell-shaped No. 3 test piece (thickness 2 mm), strain rate 120%, frequency 6. It shall be performed under the conditions of 67 Hz, 20 ° C., and a test frequency of 6.67 Hz (rotation speed: 400 rpm).
  • tie rubber is a layer formed using a rubber composition for tie rubber.
  • the rubber component of the rubber composition for tie rubber is a diene rubber, and examples thereof include natural rubber, isoprene rubber, butadiene rubber, styrene-butadiene rubber, and acrylonitrile-butadiene rubber.
  • the diene rubber constituting the tie rubber can increase the affinity with the carcass layer by using the diene rubber of the rubber composition constituting the adjacent carcass layer as a main component.
  • the rubber composition for tie rubber can increase the rubber hardness of the rubber composition for tie rubber by blending carbon black with the above-described diene rubber.
  • the carbon black is preferably blended in an amount of 40 to 70 parts by mass, more preferably 50 to 60 parts by mass with respect to 100 parts by mass of the diene rubber. By setting the blending amount of carbon black within such a range, rubber hardness can be ensured.
  • the nitrogen adsorption specific surface area of carbon black compounded in the rubber composition for tie rubber is not particularly limited, but is preferably 20 to 60 m 2 / g, more preferably 30 to 50 m 2 / g. By setting the nitrogen adsorption specific surface area of carbon black constituting the tie rubber within such a range, the rubber hardness can be easily adjusted.
  • the ratio HS T / HS IL of the rubber hardness HS T of the rubber composition for tie rubber to the rubber hardness HS IL of the rubber composition for the inner liner is not particularly limited, 1.1 or more, more preferably 1.12 to 1.25.
  • the rubber hardness ratio HS T / HS IL is 1.1 or more, the steering stability can be further improved when the tire is formed.
  • the rubber hardness HS IL of the inner liner rubber composition may be reduced by reducing the blending amount of carbon black and zinc oxide in the rubber composition for the inner liner as compared with the conventional rubber composition.
  • the steering stability can be maintained at a good level when a pneumatic tire is formed. it can.
  • the rubber composition for the inner liner and the rubber composition for the tie rubber are vulcanized or cross-linking agent, vulcanization accelerator, anti-aging agent, plasticizer, processing aid, liquid polymer, terpene resin, thermosetting
  • Various additives generally used in tire rubber compositions such as resins can be blended within a range that does not impair the object of the present invention, and such additives are kneaded by a general method to form a rubber composition. And can be used for vulcanization or crosslinking. As long as the amount of these additives is not contrary to the object of the present invention, a conventional general amount can be used.
  • the pneumatic tire of the present invention can be produced by mixing the above components using a normal rubber kneading machine such as a Banbury mixer, a kneader, or a roll.
  • the pneumatic tire of the present invention can have an excellent balance between air permeation prevention performance, steering stability and resistance to crack growth in a low temperature environment.
  • Rubber composition for inner liner As rubber compositions for forming an inner liner, 14 types of rubber compositions for inner liners having the formulations shown in Tables 1 and 2 (Examples 1 to 7, Standard Examples, Comparative Examples 1 to 6) The components excluding sulfur and vulcanization accelerator were kneaded with a 1.8 L closed mixer for 5 minutes and released to obtain a master batch. 14 types of rubber compositions for inner liners were prepared by adding sulfur and a vulcanization accelerator to the obtained master batch and mixing with an open roll.
  • rubber test pieces were prepared by vulcanization at 180 ° C. for 10 minutes in a mold having a predetermined shape.
  • the dynamic storage elastic modulus (E ′), constant strain fatigue test, crack growth resistance and rubber hardness (HS IL ) were evaluated.
  • Rubber composition for tie rubber As a rubber composition for forming tie rubber, a rubber composition for tie rubber having the composition shown in Table 3 was kneaded for 5 minutes with a 1.8 L sealed mixer except for sulfur and vulcanization accelerator. Released into a master batch. A rubber composition for tie rubber was prepared by adding sulfur and a vulcanization accelerator to the obtained master batch and mixing with an open roll. Using the obtained rubber composition for tie rubber, a rubber test piece was prepared by vulcanization at 180 ° C. for 10 minutes in a mold having a predetermined shape, and the rubber hardness (HS T ) was evaluated by the following method. Went.
  • Constant strain fatigue test Using the obtained rubber test piece, a dumbbell-shaped No. 3 test piece was prepared according to JIS K6251, and 20 ° C, strain 120%, test frequency 6 with reference to JIS-K6270. A tensile constant strain fatigue test was performed under the condition of .67 Hz (rotation speed: 400 rpm), and the number of repeated deformations until failure was measured. The obtained results are listed in the column of “Number of constant strain fatigue fractures” in Tables 1 and 2.
  • A Number of cracks is small (less than about 10)
  • B Many cracks (approximately 10 or more and less than 100)
  • C Innumerable cracks (approximately 100 or more)
  • 0 No cracks are observed with the naked eye and a 10x magnifier.
  • 1 Although not visible with the naked eye, it is recognized that there is a crack with a 10x magnifier.
  • 2 Cracks are observed with the naked eye.
  • 3 Cracks are observed with the naked eye and are deep and relatively large (less than 1 mm in length). 4: A deep and large crack (length of less than 1 to 3 mm) is confirmed.
  • 5 A crack having a length of 3 mm or more is confirmed, or the test piece is cut.
  • Rubber hardness Rubber test pieces of the obtained inner liner rubber composition and tie rubber rubber composition were used and the rubber hardness of the inner liner rubber composition (HS IL ) at 20 ° C. according to JIS K6253 according to durometer type A.
  • the rubber hardness (HS T ) of the rubber composition for tie rubber was measured, and the rubber hardness ratio HS T / HS IL was calculated.
  • the obtained results are shown in the column of “Rubber hardness ratio HS T / HS IL ” in Tables 1 and 2. The larger this value, the better the steering stability when using a tire.
  • a pneumatic tire having a tire size of 205 / 60R16 was produced in which an inner liner was formed from the obtained rubber composition for an inner liner and tie rubber was formed from a rubber composition for a tie rubber.
  • the steering stability of the obtained pneumatic tire was evaluated by the method shown below.
  • the obtained pneumatic tire is mounted on a rim (16 ⁇ 6J), mounted on a domestic 2.5 liter class test vehicle, running on a test course at 80 km / h under conditions of an air pressure of 200 kPa, Sensitivity evaluation (1-10 ratings) was conducted by 3 expert panelists.
  • the obtained results are listed in the column “Steering stability” in Tables 1 and 2. The larger this index, the better the steering stability.
  • Sulfur Sulfax 5 manufactured by Tsurumi Chemical Co., Ltd.
  • Vulcanization accelerator 1 DM-PO manufactured by Ouchi Shinsei Chemical Co., Ltd.
  • Vulcanization accelerator 2 Noxeller NS-P manufactured by Ouchi Shinsei Chemical Co., Ltd.
  • the blending amount of zinc oxide in the rubber composition for the inner liner exceeds 1.8 parts by mass, and the dynamic storage elastic modulus at ⁇ 45 ° C. exceeds 600 MPa.
  • the crack resistance performance at low temperatures also decreases.
  • the compounding amount of the resin of the rubber composition for the inner liner exceeds 13 parts by mass, and the dynamic storage elastic modulus at ⁇ 45 ° C. exceeds 600 MPa.
  • Lower crack resistance performance is also reduced.
  • the blending amount of carbon black in the rubber composition for the inner liner is less than 25 parts by mass, the steering stability is lowered.
  • the amount of carbon black in the rubber composition for the inner liner exceeds 75 parts by mass, and the dynamic storage elastic modulus at ⁇ 45 ° C. exceeds 600 MPa. descend.
  • the content of butyl halide in the rubber composition for the inner liner is less than 50% by mass, the rubber hardness is lowered and the steering stability is lowered. Moreover, the air permeation resistance is insufficient.
  • the dynamic storage elastic modulus at ⁇ 45 ° C. exceeded 600 MPa, and the crack resistance performance at low temperatures was lowered.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Tires In General (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Provided is a pneumatic tire which has improved handling stability and crack growth resistance in a low-temperature environment compared to the conventional level. The pneumatic tire has an inner liner and a tie rubber, and is characterized in that the inner liner includes a rubber composition for inner liners, which contains, in 100 parts by mass of a diene rubber containing 50-100 parts by mass of a halogenated butyl rubber, 25-75 parts by mass of a carbon black having a nitrogen adsorption specific surface area of 25-95 m2/g, 1-13 parts by mass of a resin, and 0.1-1.8 parts by mass of zinc oxide. The rubber composition has a dynamic storage modulus of 600 MPa or less at -45°C.

Description

空気入りタイヤPneumatic tire
　本発明は、操縦安定性および低温環境での耐クラック成長性を改良するようにした空気入りタイヤに関する。 The present invention relates to a pneumatic tire in which handling stability and crack growth resistance in a low temperature environment are improved.
　空気入りタイヤのインナーライナーには、耐空気透過性に優れることに加え、低発熱性、高硬度、耐クラック成長性に優れることが求められる。低発熱性、高硬度および耐クラック成長性は、空気入りタイヤの低燃費性能、操縦安定性および耐久性に影響を及ぼす重要な特性である。 ¡Inner liners for pneumatic tires are required to have excellent heat permeability, low heat buildup, high hardness, and excellent crack growth resistance. Low heat generation, high hardness, and crack growth resistance are important characteristics that affect the low fuel consumption performance, steering stability and durability of pneumatic tires.
　従来、インナーライナー用ゴム組成物の硬度を高くするため、ハロゲン化ブチルゴムへの酸化亜鉛および石油系樹脂の配合量を多くすることが知られている。しかし、酸化亜鉛の分散不良や石油系樹脂が多くなることによりゴム組成物のガラス転移温度Ｔｇが高くなり、低温環境における耐クラック性が低下することが懸念される。このため、ゴム硬度を高くし操縦安定性を確保することと、低温環境下の耐クラック性能を確保することとを高次に両立させることは困難であった。 Conventionally, in order to increase the hardness of the rubber composition for the inner liner, it is known to increase the blending amount of zinc oxide and petroleum resin into the halogenated butyl rubber. However, there is concern that the glass transition temperature Tg of the rubber composition is increased due to poor dispersion of zinc oxide and an increase in petroleum-based resin, and crack resistance in a low temperature environment is lowered. For this reason, it has been difficult to achieve both higher order to increase rubber hardness and ensure steering stability and to ensure crack resistance performance in a low temperature environment.
　特許文献１は、操縦安定性、低燃費性、空気遮断性を改善するため、再生ブチルゴム、ハロゲン化ブチルゴムに瀝青炭粉砕物、タルク、マイカ及びハードクレーからなる群より選択される少なくとも一種の弱補強性フィラーと、窒素吸着比表面積が２０～３５ｍ2／ｇのカーボンブラック、酸化亜鉛および混合樹脂を配合したインナーライナー用ゴム組成物を記載する。しかし、このゴム組成物を使用した空気入りタイヤでも、操縦安定性および低温環境下の耐クラック成長性を高次に両立させることは困難であった。 Patent Document 1 discloses at least one weak reinforcement selected from the group consisting of recycled butyl rubber, halogenated butyl rubber, bituminous coal pulverized material, talc, mica, and hard clay in order to improve handling stability, fuel efficiency, and air barrier properties. A rubber composition for an inner liner is described in which a functional filler, carbon black having a nitrogen adsorption specific surface area of 20 to 35 m 2 / g, zinc oxide, and a mixed resin are blended. However, even with a pneumatic tire using this rubber composition, it has been difficult to achieve both high driving stability and crack growth resistance in a low temperature environment.
日本国特許第５７４５４９０号公報Japanese Patent No. 5745490
　本発明の目的は、操縦安定性および低温環境での耐クラック成長性を従来レベル以上に向上させるようにした空気入りタイヤを提供することにある。 An object of the present invention is to provide a pneumatic tire in which the handling stability and the crack growth resistance in a low temperature environment are improved to the conventional level or more.
　上記目的を達成する本発明の空気入りタイヤは、インナーライナーおよびタイゴムを有する空気入りタイヤであって、前記インナーライナーを構成するインナーライナー用ゴム組成物が、ハロゲン化ブチルゴムを５０～１００質量部含むジエン系ゴム１００質量部に、窒素吸着比表面積が２５～９５ｍ2／ｇであるカーボンブラックを２５～７５質量部、樹脂を１～１３質量部、酸化亜鉛を０．１～１．８質量部配合してなり、その－４５℃における動的貯蔵弾性率が６００ＭＰａ以下であることを特徴とする。 The pneumatic tire of the present invention that achieves the above object is a pneumatic tire having an inner liner and a tie rubber, wherein the rubber composition for the inner liner constituting the inner liner contains 50 to 100 parts by mass of a halogenated butyl rubber. 100 parts by mass of diene rubber, 25 to 75 parts by mass of carbon black having a nitrogen adsorption specific surface area of 25 to 95 m 2 / g, 1 to 13 parts by mass of resin, and 0.1 to 1.8 parts by mass of zinc oxide The dynamic storage elastic modulus at −45 ° C. is 600 MPa or less.
　本発明の空気入りタイヤは、ハロゲン化ブチルゴムを５０～１００質量部含むジエン系ゴム１００質量部に、特定のカーボンブラックを２５～７５質量部、樹脂を１～１３質量部、酸化亜鉛を０．１～１．８質量部配合したインナーライナー用ゴム組成物の－４５℃における動的貯蔵弾性率を６００ＭＰａ以下にしたので、操縦安定性および低温環境での耐クラック成長性を従来レベル以上に向上させることができる。 In the pneumatic tire of the present invention, 100 parts by mass of a diene rubber containing 50 to 100 parts by mass of a halogenated butyl rubber, 25 to 75 parts by mass of specific carbon black, 1 to 13 parts by mass of resin, and 0.1% of zinc oxide. The dynamic storage elastic modulus at −45 ° C. of the rubber composition for the inner liner compounded with 1 to 1.8 parts by mass is reduced to 600 MPa or less, so that the handling stability and the crack growth resistance in a low temperature environment are improved to the conventional level or more. Can be made.
　前記インナーライナー用ゴム組成物のひずみ率１２０％、周波数６．６７Ｈｚの定歪疲労試験における破壊繰り返し変形回数が８００，０００回以上であるとよい。 The number of repeated repeated deformations in the constant strain fatigue test with a strain rate of 120% and a frequency of 6.67 Hz of the rubber composition for the inner liner is preferably 800,000 times or more.
　前記インナーライナー用ゴム組成物のゴム硬度ＨＳILに対する、前記タイゴムを構成するタイゴム用ゴム組成物のゴム硬度ＨＳTの比ＨＳT／ＨＳILを１．１以上にすることにより、操縦安定性および耐クラック性能のバランスをより優れたものにすることができる。 To rubber hardness HS IL of the rubber composition for an inner liner, by the ratio HS T / HS IL rubber hardness HS T 1.1 or more tie rubber for the rubber composition constituting the tie rubber, steering stability and The balance of crack resistance performance can be further improved.
図１は、本発明の空気入りタイヤの実施形態の一例を示す子午線方向の断面図である。FIG. 1 is a cross-sectional view in the meridian direction showing an example of an embodiment of a pneumatic tire of the present invention.
　図１において、空気入りタイヤは、トレッド部１、サイド部２及びビード部３を有し、左右のビード部３，３間にカーカス層４が装架され、その両端部がビードコア５の周りにタイヤ内側から外側に折り返されている。トレッド部１におけるカーカス層４のタイヤ径方向外側にはベルト層６が配置され、そのベルト層６の外側にトレッドゴム９が配置される。またカーカス層４のタイヤ径方向内側にはタイゴム７が配置され、更にその内側にインナーライナー８が配置される。インナーライナー８は、インナーライナー用ゴム組成物を用いて成形された層であり、タイゴム７は、タイゴム用ゴム組成物を用いて成形された層である。 In FIG. 1, the pneumatic tire has a tread portion 1, a side portion 2, and a bead portion 3, a carcass layer 4 is mounted between the left and right bead portions 3, 3, and both end portions thereof are around the bead core 5. Folded from the inside to the outside of the tire. A belt layer 6 is disposed outside the carcass layer 4 in the tire tread portion 1 in the tire radial direction, and a tread rubber 9 is disposed outside the belt layer 6. Further, a tie rubber 7 is disposed on the inner side of the carcass layer 4 in the tire radial direction, and an inner liner 8 is further disposed on the inner side. The inner liner 8 is a layer molded using a rubber composition for an inner liner, and the tie rubber 7 is a layer molded using a rubber composition for a tie rubber.
　インナーライナー用ゴム組成物のゴム成分はジエン系ゴムであり、ハロゲン化ブチルゴムを含む。ハロゲン化ブチルゴムの含有量は、ジエン系ゴム１００質量％中５０～１００質量％、好ましくは６０～８０質量％である。ハロゲン化ブチルゴムの含有量を５０質量％以上にすることにより、空気透過防止性能を確保することができる。ハロゲン化ブチルゴムとして、臭素化ブチルゴム、塩素化ブチルゴム等を例示することができる。 The rubber component of the rubber composition for the inner liner is a diene rubber and includes a halogenated butyl rubber. The content of the halogenated butyl rubber is 50 to 100% by mass, preferably 60 to 80% by mass, in 100% by mass of the diene rubber. By setting the content of halogenated butyl rubber to 50% by mass or more, air permeation preventing performance can be ensured. Examples of the halogenated butyl rubber include brominated butyl rubber and chlorinated butyl rubber.
　ジエン系ゴムは、ハロゲン化ブチルゴム以外の他のジエン系ゴムを含有することができる。他のジエン系ゴムとして、例えばブチルゴム、天然ゴム、イソプレンゴム、ブタジエンゴム、スチレン－ブタジエンゴム、アクリロニトリル－ブタジエンゴム等が挙げられ、単独又は複数のブレンドとして使用することができる。 The diene rubber can contain other diene rubbers other than the halogenated butyl rubber. Examples of other diene rubbers include butyl rubber, natural rubber, isoprene rubber, butadiene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, and the like, and they can be used alone or as a blend.
　インナーライナー用ゴム組成物は、カーボンブラックを配合することにより、ゴム硬度および耐クラック成長性を高くする。カーボンブラックの配合量は、ジエン系ゴム１００質量部に対し２５～７５質量部、好ましくは３０～７０質量部である。カーボンブラックの配合量が２５質量部未満であると、ゴム組成物のゴム硬度が十分に得られず、操縦安定性が低下する。またカーボンブラックの配合量が７５質量部を超えると、－４５℃における動的貯蔵弾性率が大きくなり耐クラック成長性が低下する。 The rubber composition for the inner liner increases the rubber hardness and the crack growth resistance by adding carbon black. The compounding amount of carbon black is 25 to 75 parts by mass, preferably 30 to 70 parts by mass with respect to 100 parts by mass of the diene rubber. When the blending amount of carbon black is less than 25 parts by mass, the rubber hardness of the rubber composition cannot be sufficiently obtained, and the steering stability is lowered. On the other hand, when the blending amount of the carbon black exceeds 75 parts by mass, the dynamic storage elastic modulus at −45 ° C. increases and the crack growth resistance decreases.
　本発明で使用するカーボンブラックは、窒素吸着比表面積Ｎ2ＳＡが２５～９５ｍ2／ｇ、好ましくは３０～５５ｍ2／ｇである。Ｎ2ＳＡが２５ｍ2／ｇ未満であると、インナーライナー用ゴム組成物のゴム硬度、動的弾性率などの機械的特性が低下し、耐クラック成長性が不足する虞がある。Ｎ2ＳＡが９５ｍ2／ｇを超えると、転がり抵抗が大きくなる。また耐クラック成長性が低下する。このようなカーボンブラックは、ＨＡＦ級～ＧＰＦ級のなかから適宜、選んで使用することができる。カーボンブラックのＮ2ＳＡは、ＪＩＳ　Ｋ６２１７－２に準拠して、測定するものとする。 Carbon black used in the present invention, the nitrogen adsorption specific surface area N 2 SA is 25 ~ 95m 2 / g, preferably from 30 ~ 55m 2 / g. When N 2 SA is less than 25 m 2 / g, mechanical properties such as rubber hardness and dynamic elastic modulus of the rubber composition for the inner liner are lowered, and there is a fear that the crack growth resistance is insufficient. When N 2 SA exceeds 95 m 2 / g, rolling resistance increases. Moreover, crack growth resistance falls. Such carbon black can be appropriately selected and used from HAF class to GPF class. The N 2 SA of carbon black shall be measured according to JIS K6217-2.
　本発明において、インナーライナー用ゴム組成物は樹脂を含む。樹脂として、石油系樹脂および／または芳香族系樹脂が挙げられる。樹脂を配合することにより、インナーライナー用ゴム組成物のゴム硬度およびゴム－ゴム間の剥離接着力を改良することができる。樹脂の配合量は、ジエン系ゴム１００質量部に対し１～１３質量部、好ましくは３～１０質量部である。樹脂の配合量が１質量部未満であると、ゴム硬度を十分に改良することができない。また樹脂の配合量が１３質量部を超えると、－４５℃における動的貯蔵弾性率が大きくなり耐クラック成長性が却って低下する。また空気透過防止性能が低下する虞がある。 In the present invention, the rubber composition for the inner liner includes a resin. Examples of the resin include petroleum resins and / or aromatic resins. By blending the resin, it is possible to improve the rubber hardness of the rubber composition for the inner liner and the adhesive strength between rubber and rubber. The compounding amount of the resin is 1 to 13 parts by mass, preferably 3 to 10 parts by mass with respect to 100 parts by mass of the diene rubber. When the blending amount of the resin is less than 1 part by mass, the rubber hardness cannot be sufficiently improved. On the other hand, when the amount of the resin exceeds 13 parts by mass, the dynamic storage elastic modulus at −45 ° C. increases and crack growth resistance decreases. Moreover, there exists a possibility that the air permeation prevention performance may fall.
　石油系樹脂は、原油を蒸留、分解、改質などの処理をして得られた成分を重合して製造される芳香族系炭化水素樹脂、または飽和あるいは不飽和脂肪族系炭化水素樹脂である。石油系樹脂として、例えばＣ５系石油樹脂（イソプレン、１，３－ペンタジエン、シクロペンタジエン、メチルブテン、ペンテンなどの留分を重合した脂肪族系石油樹脂）、Ｃ９系石油樹脂（α－メチルスチレン、ｏ－ビニルトルエン、ｍ－ビニルトルエン、ｐ－ビニルトルエンなどの留分を重合した芳香族系石油樹脂）、Ｃ５Ｃ９共重合石油樹脂などが例示される。 Petroleum resins are aromatic hydrocarbon resins or saturated or unsaturated aliphatic hydrocarbon resins produced by polymerizing components obtained by subjecting crude oil to distillation, decomposition, reforming, and the like. . Examples of petroleum resins include C5 petroleum resins (aliphatic petroleum resins obtained by polymerizing fractions such as isoprene, 1,3-pentadiene, cyclopentadiene, methylbutene, and pentene), C9 petroleum resins (α-methylstyrene, o -Aromatic petroleum resin obtained by polymerizing a fraction such as vinyltoluene, m-vinyltoluene, p-vinyltoluene), C5C9 copolymerized petroleum resin, and the like.
　また芳香族系樹脂は、芳香族系炭化水素からなるセグメントを少なくとも１つ有する重合体であり、クマロン樹脂、フェノール樹脂、アルキルフェノール樹脂、テルペン系樹脂、ロジン系樹脂、ノボラック系樹脂、レゾール系樹脂などをあげることができる。これらの樹脂は、単独又は複数のブレンドとして使用することができる。なお上述したＣ９系石油樹脂は、芳香族系炭化水素樹脂であるが、本明細書では石油系樹脂に分類するものとする。 The aromatic resin is a polymer having at least one segment composed of an aromatic hydrocarbon, such as coumarone resin, phenol resin, alkylphenol resin, terpene resin, rosin resin, novolac resin, resole resin, etc. Can give. These resins can be used alone or as a blend. The C9 petroleum resin described above is an aromatic hydrocarbon resin, but is classified as a petroleum resin in this specification.
　本発明において、インナーライナー用ゴム組成物は、酸化亜鉛をジエン系ゴム１００質量部に対し０．１～１．８質量部、好ましくは０．２～１．６質量部配合する。酸化亜鉛を配合することにより、ゴム硬度を確保し操縦安定性を優れたものにすることができる。酸化亜鉛の配合量が０．１質量部未満であると、ゴム硬度が不足する。また酸化亜鉛の配合量が１．８質量部を超えると、－４５℃における動的貯蔵弾性率が大きくなり耐クラック成長性が低下する。また操縦安定性が却って低下する。 In the present invention, the rubber composition for the inner liner is blended with 0.1 to 1.8 parts by mass, preferably 0.2 to 1.6 parts by mass of zinc oxide with respect to 100 parts by mass of the diene rubber. By blending zinc oxide, rubber hardness can be secured and steering stability can be improved. When the blending amount of zinc oxide is less than 0.1 parts by mass, the rubber hardness is insufficient. On the other hand, when the blending amount of zinc oxide exceeds 1.8 parts by mass, the dynamic storage elastic modulus at −45 ° C. is increased and the crack growth resistance is lowered. In addition, steering stability is reduced.
　インナーライナー用ゴム組成物の－４５℃における動的貯蔵弾性率は６００ＭＰａ以下、好ましくは４１０～５９０ＭＰａである。－４５℃における動的貯蔵弾性率を６００ＭＰａ以下にすることにより、空気入りタイヤの低温環境下における耐クラック成長性を改良し優れたものにすることができる。本明細書において、－４５℃における動的貯蔵弾性率は、初期歪み１０％、動歪み±２％、周波数２０Ｈｚ、温度－４５℃の条件下で測定するものとする。 The dynamic storage elastic modulus at −45 ° C. of the rubber composition for the inner liner is 600 MPa or less, preferably 410 to 590 MPa. By setting the dynamic storage elastic modulus at −45 ° C. to 600 MPa or less, the crack growth resistance in a low temperature environment of a pneumatic tire can be improved and improved. In this specification, the dynamic storage elastic modulus at −45 ° C. is measured under conditions of an initial strain of 10%, a dynamic strain of ± 2%, a frequency of 20 Hz, and a temperature of −45 ° C.
　インナーライナー用ゴム組成物の定歪疲労試験における破壊繰り返し変形回数は、好ましくは８００，０００回以上、より好ましくは８１０，０００～９９０，０００回であるとよい。定歪疲労の破壊繰り返し変形回数を８００，０００回以上にすることにより、タイヤ耐久性を優れたものにすることができる。本明細書において、定歪疲労試験は、ＪＩＳ－Ｋ６２７０に記載された引張疲労特性を参考にして、ダンベル状３号形の試験片（厚さ２ｍｍ）を用い、ひずみ率１２０％、周波数６．６７Ｈｚ、２０℃、試験周波数６．６７Ｈｚ（回転数４００ｒｐｍ）の条件で行うものとする。 The number of repeated repeated deformations in the constant strain fatigue test of the rubber composition for the inner liner is preferably 800,000 times or more, more preferably 810,000 to 990,000 times. By making the number of repeated repeated deformations of constant strain fatigue 800,000 times or more, tire durability can be improved. In this specification, the constant strain fatigue test is based on tensile fatigue characteristics described in JIS-K6270, using a dumbbell-shaped No. 3 test piece (thickness 2 mm), strain rate 120%, frequency 6. It shall be performed under the conditions of 67 Hz, 20 ° C., and a test frequency of 6.67 Hz (rotation speed: 400 rpm).
　本発明の空気入りタイヤにおいて、タイゴムは、タイゴム用ゴム組成物を用いて成形された層である。タイゴム用ゴム組成物のゴム成分はジエン系ゴムであり、例えば、天然ゴム、イソプレンゴム、ブタジエンゴム、スチレン－ブタジエンゴム、アクリロニトリル－ブタジエンゴム等が挙げられる。タイゴムを構成するジエン系ゴムは、隣接するカーカス層を構成するゴム組成物のジエン系ゴムを主成分にすることにより、カーカス層との親和性を高くすることができる。 In the pneumatic tire of the present invention, tie rubber is a layer formed using a rubber composition for tie rubber. The rubber component of the rubber composition for tie rubber is a diene rubber, and examples thereof include natural rubber, isoprene rubber, butadiene rubber, styrene-butadiene rubber, and acrylonitrile-butadiene rubber. The diene rubber constituting the tie rubber can increase the affinity with the carcass layer by using the diene rubber of the rubber composition constituting the adjacent carcass layer as a main component.
　タイゴム用ゴム組成物は、上述したジエン系ゴムに、カーボンブラックを配合することにより、タイゴム用ゴム組成物のゴム硬度を高くすることができる。カーボンブラックは、ジエン系ゴム１００質量部に対し好ましくは４０～７０質量部、より好ましくは５０～６０質量部配合するとよい。カーボンブラックの配合量をこのような範囲内にすることにより、ゴム硬度を確保することができる。 The rubber composition for tie rubber can increase the rubber hardness of the rubber composition for tie rubber by blending carbon black with the above-described diene rubber. The carbon black is preferably blended in an amount of 40 to 70 parts by mass, more preferably 50 to 60 parts by mass with respect to 100 parts by mass of the diene rubber. By setting the blending amount of carbon black within such a range, rubber hardness can be ensured.
　タイゴム用ゴム組成物に配合するカーボンブラックの窒素吸着比表面積は、特に制限されるものではないが、好ましくは２０～６０ｍ2／ｇ、より好ましくは３０～５０ｍ2／ｇであるとよい。タイゴムを構成するカーボンブラックの窒素吸着比表面積をこのような範囲内にすることにより、ゴム硬度を調節しやすくなる。 The nitrogen adsorption specific surface area of carbon black compounded in the rubber composition for tie rubber is not particularly limited, but is preferably 20 to 60 m 2 / g, more preferably 30 to 50 m 2 / g. By setting the nitrogen adsorption specific surface area of carbon black constituting the tie rubber within such a range, the rubber hardness can be easily adjusted.
　本発明の空気入りタイヤにおいて、インナーライナー用ゴム組成物のゴム硬度ＨＳILに対するタイゴム用ゴム組成物のゴム硬度ＨＳTの比ＨＳT／ＨＳILは、特に制限されるものではないが、好ましくは１．１以上、より好ましくは１．１２～１．２５であるとよい。ゴム硬度の比ＨＳT／ＨＳILを１．１以上にすることにより、タイヤにしたとき操縦安定性をより優れたものにすることができる。特に、インナーライナー用ゴム組成物におけるカーボンブラックおよび酸化亜鉛の配合量を、従来より少なくすることにより、インナーライナー用ゴム組成物のゴム硬度ＨＳILが小さくなることが懸念されるが、ゴム硬度の比ＨＳT／ＨＳILが１．１以上になるように、タイゴム用ゴム組成物のゴム硬度ＨＳTを高くすることにより、空気入りタイヤにしたとき操縦安定性を良好なレベルに維持することができる。 In the pneumatic tire of the present invention, the ratio HS T / HS IL of the rubber hardness HS T of the rubber composition for tie rubber to the rubber hardness HS IL of the rubber composition for the inner liner is not particularly limited, 1.1 or more, more preferably 1.12 to 1.25. By setting the rubber hardness ratio HS T / HS IL to 1.1 or more, the steering stability can be further improved when the tire is formed. In particular, there is a concern that the rubber hardness HS IL of the inner liner rubber composition may be reduced by reducing the blending amount of carbon black and zinc oxide in the rubber composition for the inner liner as compared with the conventional rubber composition. By increasing the rubber hardness HS T of the rubber composition for tie rubber so that the ratio HS T / HS IL is 1.1 or more, the steering stability can be maintained at a good level when a pneumatic tire is formed. it can.
　本発明において、インナーライナー用ゴム組成物及びタイゴム用ゴム組成物は、加硫又は架橋剤、加硫促進剤、老化防止剤、可塑剤、加工助剤、液状ポリマー、テルペン系樹脂、熱硬化性樹脂などのタイヤ用ゴム組成物に一般的に使用される各種添加剤を、本発明の目的を阻害しない範囲内で配合することができ、かかる添加剤は一般的な方法で混練してゴム組成物とし、加硫又は架橋するのに使用することができる。これらの添加剤の配合量は本発明の目的に反しない限り、従来の一般的な配合量とすることができる。本発明の空気入りタイヤは、通常のゴム用混練機械、例えば、バンバリーミキサー、ニーダー、ロール等を使用して、上記各成分を混合することによって製造することができる。 In the present invention, the rubber composition for the inner liner and the rubber composition for the tie rubber are vulcanized or cross-linking agent, vulcanization accelerator, anti-aging agent, plasticizer, processing aid, liquid polymer, terpene resin, thermosetting Various additives generally used in tire rubber compositions such as resins can be blended within a range that does not impair the object of the present invention, and such additives are kneaded by a general method to form a rubber composition. And can be used for vulcanization or crosslinking. As long as the amount of these additives is not contrary to the object of the present invention, a conventional general amount can be used. The pneumatic tire of the present invention can be produced by mixing the above components using a normal rubber kneading machine such as a Banbury mixer, a kneader, or a roll.
　本発明の空気入りタイヤは、空気透過防止性能と、操縦安定性および低温環境下での耐クラック成長性とのバランスを優れたものにすることができる。 The pneumatic tire of the present invention can have an excellent balance between air permeation prevention performance, steering stability and resistance to crack growth in a low temperature environment.
　以下、実施例によって本発明をさらに説明するが、本発明の範囲はこれらの実施例に限定されるものではない。 Hereinafter, the present invention will be further described with reference to examples, but the scope of the present invention is not limited to these examples.
　　　インナーライナー用ゴム組成物
　インナーライナーを形成するゴム組成物として、表１，２に示す配合からなる１４種類のインナーライナー用ゴム組成物（実施例１～７、標準例、比較例１～６）を、硫黄、加硫促進剤を除く成分を１.８Ｌの密閉型ミキサーで５分間混練し放出しマスターバッチとした。得られたマスターバッチに、硫黄、加硫促進剤を加えてオープンロールで混合することにより、１４種類のインナーライナー用ゴム組成物を調製した。 Rubber composition for inner liner As rubber compositions for forming an inner liner, 14 types of rubber compositions for inner liners having the formulations shown in Tables 1 and 2 (Examples 1 to 7, Standard Examples, Comparative Examples 1 to 6) The components excluding sulfur and vulcanization accelerator were kneaded with a 1.8 L closed mixer for 5 minutes and released to obtain a master batch. 14 types of rubber compositions for inner liners were prepared by adding sulfur and a vulcanization accelerator to the obtained master batch and mixing with an open roll.
　得られた１４種類のインナーライナー用ゴム組成物を使用して、所定形状の金型中で、１８０℃、１０分間加硫してゴム試験片を作製し、下記に示す方法により－４５℃の動的貯蔵弾性率（Ｅ′）、定歪疲労試験、耐クラック成長性およびゴム硬度（ＨＳIL）の評価を行った。 Using the obtained 14 types of rubber compositions for inner liners, rubber test pieces were prepared by vulcanization at 180 ° C. for 10 minutes in a mold having a predetermined shape. The dynamic storage elastic modulus (E ′), constant strain fatigue test, crack growth resistance and rubber hardness (HS IL ) were evaluated.
　　　タイゴム用ゴム組成物
　タイゴムを形成するゴム組成物として、表３に示す配合からなるタイゴム用ゴム組成物を、硫黄、加硫促進剤を除く成分を１.８Ｌの密閉型ミキサーで５分間混練し放出しマスターバッチとした。得られたマスターバッチに、硫黄、加硫促進剤を加えてオープンロールで混合することにより、タイゴム用ゴム組成物を調製した。得られたタイゴム用ゴム組成物を使用して、所定形状の金型中で、１８０℃、１０分間加硫してゴム試験片を作製し、下記に示す方法によりゴム硬度（ＨＳT）の評価を行った。 Rubber composition for tie rubber As a rubber composition for forming tie rubber, a rubber composition for tie rubber having the composition shown in Table 3 was kneaded for 5 minutes with a 1.8 L sealed mixer except for sulfur and vulcanization accelerator. Released into a master batch. A rubber composition for tie rubber was prepared by adding sulfur and a vulcanization accelerator to the obtained master batch and mixing with an open roll. Using the obtained rubber composition for tie rubber, a rubber test piece was prepared by vulcanization at 180 ° C. for 10 minutes in a mold having a predetermined shape, and the rubber hardness (HS T ) was evaluated by the following method. Went.
　　　－４５℃の動的貯蔵弾性率（Ｅ′）
　得られたゴム試験片をＪＩＳ　Ｋ６３９４に準拠して、東洋精機製作所社製粘弾性スペクトロメーターを用いて、初期歪み１０％、動歪±２％、周波数２０Ｈｚの条件で、温度－４５℃における動的貯蔵弾性率（Ｅ′）を測定した。得られたＥ′の結果は、表１，２の「Ｅ′（－４５℃）」の欄に示した。 Dynamic storage elastic modulus (E ') at -45 ° C
Using the viscoelastic spectrometer manufactured by Toyo Seiki Seisakusho Co., Ltd., the obtained rubber test piece was subjected to a dynamic test at a temperature of −45 ° C. under conditions of an initial strain of 10%, a dynamic strain of ± 2%, and a frequency of 20 Hz. The storage elastic modulus (E ') was measured. The obtained E ′ results are shown in the column “E ′ (−45 ° C.)” in Tables 1 and 2.
　　　定歪疲労試験
　得られたゴム試験片を使用し、ＪＩＳ　Ｋ６２５１に準拠して、ダンベル状３号形試験片を作製し、ＪＩＳ－Ｋ６２７０を参考にして、２０℃、歪１２０％、試験周波数６．６７Ｈｚ（回転数４００ｒｐｍ）の条件で引張定歪疲労試験を行い、破壊するまでの繰り返し変形回数を測定した。得られた結果は、表１，２の「定歪疲労　破壊変形数」の欄に記載した。 Constant strain fatigue test Using the obtained rubber test piece, a dumbbell-shaped No. 3 test piece was prepared according to JIS K6251, and 20 ° C, strain 120%, test frequency 6 with reference to JIS-K6270. A tensile constant strain fatigue test was performed under the condition of .67 Hz (rotation speed: 400 rpm), and the number of repeated deformations until failure was measured. The obtained results are listed in the column of “Number of constant strain fatigue fractures” in Tables 1 and 2.
　　　耐クラック成長性
　得られたゴム試験片からＪＩＳ　Ｋ６２５１に準拠したダンベル状３号形試験片を切り出した。この試験片をＪＩＳ　Ｋ６２６０に準拠し、デマチャ屈曲き裂試験機を用いて、温度－４５℃、ストローク５７ｍｍ、速度３００±１０ｒｐｍ、屈曲回数１０万回の条件で、繰り返し屈曲によるき裂成長の長さを測定し、その後、試験片表面の亀裂（クラック）の有無を目視で観察し以下のＡ～Ｃで評価すると共に、亀裂の状態を以下の１～６の判定基準に基づき６段階で評価した。得られた結果を、表１，２の「耐クラック性能」の欄に示した。
　Ａ：亀裂の数が少ない（およそ１０個未満）
　Ｂ：亀裂の数が多い（およそ１０個以上、１００個未満）
　Ｃ：亀裂が無数に存在する（およそ１００個以上）
　０：肉眼および１０倍の拡大鏡で亀裂が確認されない。
　１：肉眼では見えないが１０倍の拡大鏡で亀裂があると認められる。
　２：肉眼で亀裂が観察される。
　３：亀裂が肉眼で観察され、深くて比較的大きい（長さ１ｍｍ未満）。
　４：深くて大きい亀裂（長さ１～３ｍｍ未満）が確認される。
　５：長さ３ｍｍ以上の亀裂が確認されるか、または試験片が切断される。 Crack growth resistance A dumbbell-shaped No. 3 test piece based on JIS K6251 was cut out from the obtained rubber test piece. The length of crack growth by repeated bending of this specimen in accordance with JIS K6260, using a Demacha bending crack tester at a temperature of −45 ° C., a stroke of 57 mm, a speed of 300 ± 10 rpm, and a bending frequency of 100,000. After that, the presence or absence of cracks (cracks) on the surface of the test piece is visually observed and evaluated according to the following AC, and the crack condition is evaluated in 6 stages based on the following criteria 1 to 6 did. The obtained results are shown in the “crack resistance performance” column of Tables 1 and 2.
A: Number of cracks is small (less than about 10)
B: Many cracks (approximately 10 or more and less than 100)
C: Innumerable cracks (approximately 100 or more)
0: No cracks are observed with the naked eye and a 10x magnifier.
1: Although not visible with the naked eye, it is recognized that there is a crack with a 10x magnifier.
2: Cracks are observed with the naked eye.
3: Cracks are observed with the naked eye and are deep and relatively large (less than 1 mm in length).
4: A deep and large crack (length of less than 1 to 3 mm) is confirmed.
5: A crack having a length of 3 mm or more is confirmed, or the test piece is cut.
　　　ゴム硬度
　得られたインナーライナー用ゴム組成物およびタイゴム用ゴム組成物のゴム試験片を使用し、ＪＩＳ　Ｋ６２５３に準拠しデュロメータのタイプＡにより２０℃でインナーライナー用ゴム組成物のゴム硬度（ＨＳIL）およびタイゴム用ゴム組成物のゴム硬度（ＨＳT）を測定し、ゴム硬度の比ＨＳT／ＨＳILを算出した。得られた結果は、表１，２の「ゴム硬度比　ＨＳT／ＨＳIL」の欄に記載した。この値が大きいほど、タイヤにしたとき操縦安定性が優れることを意味する。 Rubber hardness Rubber test pieces of the obtained inner liner rubber composition and tie rubber rubber composition were used and the rubber hardness of the inner liner rubber composition (HS IL ) at 20 ° C. according to JIS K6253 according to durometer type A. The rubber hardness (HS T ) of the rubber composition for tie rubber was measured, and the rubber hardness ratio HS T / HS IL was calculated. The obtained results are shown in the column of “Rubber hardness ratio HS T / HS IL ” in Tables 1 and 2. The larger this value, the better the steering stability when using a tire.
　　　空気入りタイヤの製作
　得られたインナーライナー用ゴム組成物によりインナーライナー、タイゴム用ゴム組成物によりタイゴムを構成したタイヤサイズ２０５／６０Ｒ１６の空気入りタイヤを製作した。得られた空気入りタイヤの操縦安定性を、下記に示す方法により評価した。 Production of Pneumatic Tire A pneumatic tire having a tire size of 205 / 60R16 was produced in which an inner liner was formed from the obtained rubber composition for an inner liner and tie rubber was formed from a rubber composition for a tie rubber. The steering stability of the obtained pneumatic tire was evaluated by the method shown below.
　　　操縦安定性
　得られた空気入りタイヤをリム（１６×６Ｊ）に装着し、国産２．５リットルクラスの試験車両に装着し、空気圧２００ｋＰａの条件で、テストコースを８０ｋｍ／ｈで実車走行させ、専門パネラー３名による感応評価（１～１０の評点付け）を行った。得られた結果は、表１，２の「操縦安定性」の欄に記載した。この指数が大きいほど操縦安定性が優れていることを意味する。 Steering stability The obtained pneumatic tire is mounted on a rim (16 × 6J), mounted on a domestic 2.5 liter class test vehicle, running on a test course at 80 km / h under conditions of an air pressure of 200 kPa, Sensitivity evaluation (1-10 ratings) was conducted by 3 expert panelists. The obtained results are listed in the column “Steering stability” in Tables 1 and 2. The larger this index, the better the steering stability.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　なお、表１，２において使用した原材料の種類を下記に示す。
・ハロゲン化ブチルゴム：臭素化イソブチレンイソプレンラバー、ＥＸＸＯＮ　ＣＨＥＭＩＣＡＬ社製
・天然ゴム：ＴＳＲ２０
・カーボンブラック１：新日化カーボン社製ニテロン＃５５Ｓ、Ｎ2ＳＡが３６ｍ2／ｇ
・カーボンブラック２：キャボットジャパン社製ショウブラックＮ２３４、Ｎ2ＳＡが１２０ｍ2／ｇ
・タルク：山陽クレー工業社製カタルポＹ－Ｋ
・酸化亜鉛：正同化学工業社製酸化亜鉛３種
・樹脂：芳香族系石油樹脂、ＡＩＲ　ＷＡＴＥＲ　ＩＮＣ製
・硫黄：鶴見化学工業社製サルファックス５
・加硫促進剤１：大内新興化学工業社製ＤＭ－ＰＯ
・加硫促進剤２：大内新興化学工業社製ノクセラーＮＳ－Ｐ The types of raw materials used in Tables 1 and 2 are shown below.
· Halogenated butyl rubber: Brominated isobutylene isoprene rubber, manufactured by EXXON CHEMICAL · Natural rubber: TSR20
Carbon black 1: Nippon Carbon Co., Ltd. Niteron # 55S, N 2 SA is 36m 2 / g
Carbon black 2: Show black N234, N 2 SA manufactured by Cabot Japan, 120 m 2 / g
・ Talc: Sanyo Clay Industry Co., Ltd. Catalpo YK
・ Zinc oxide: Zinc oxide 3 types manufactured by Shodo Chemical Industry Co., Ltd. ・ Resin: aromatic petroleum resin, manufactured by AIR WATER INC. ・ Sulfur: Sulfax 5 manufactured by Tsurumi Chemical Co., Ltd.
・ Vulcanization accelerator 1: DM-PO manufactured by Ouchi Shinsei Chemical Co., Ltd.
・ Vulcanization accelerator 2: Noxeller NS-P manufactured by Ouchi Shinsei Chemical Co., Ltd.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　なお、表３において使用した原材料の種類を下記に示す。
・天然ゴム：ＴＳＲ２０
・ＳＢＲ：乳化重合スチレンブタジエンゴム日本ゼオン製Ｎｉｐｏｌ　１５０２
・カーボンブラック１：新日化カーボン社製ニテロン＃５５Ｓ、Ｎ2ＳＡが３６ｍ2／ｇ
・酸化亜鉛：正同化学工業社製酸化亜鉛３種
・硫黄：鶴見化学工業社製サルファックス５
・加硫促進剤２：大内新興化学工業社製ノクセラーＮＳ－Ｐ In addition, the kind of raw material used in Table 3 is shown below.
・ Natural rubber: TSR20
SBR: emulsion polymerization styrene butadiene rubber Nipol 1502 manufactured by Nippon Zeon
Carbon black 1: Nippon Carbon Co., Ltd. Niteron # 55S, N 2 SA is 36m 2 / g
・ Zinc oxide: 3 types of zinc oxide manufactured by Shodo Chemical Industry Co., Ltd. ・ Sulfur: Sulfax 5 manufactured by Tsurumi Chemical Industry Co., Ltd.
・ Vulcanization accelerator 2: Noxeller NS-P manufactured by Ouchi Shinsei Chemical Co., Ltd.
　表１から明らかなように実施例１～７の空気入りタイヤは、操縦安定性を従来レベル以上に向上し、かつ低温環境下における耐クラック成長性に優れることが確認された。 As is apparent from Table 1, it was confirmed that the pneumatic tires of Examples 1 to 7 improved the steering stability to the conventional level and had excellent crack growth resistance under a low temperature environment.
　比較例１の空気入りタイヤは、インナーライナー用ゴム組成物の酸化亜鉛の配合量が１．８質量部を超え、－４５℃の動的貯蔵弾性率が６００ＭＰａを超えるので、操縦安定性が低下し、低温下の耐クラック性能も低下する。
　比較例２の空気入りタイヤは、インナーライナー用ゴム組成物の樹脂の配合量が１３質量部を超え、－４５℃の動的貯蔵弾性率が６００ＭＰａを超えるので、操縦安定性が低下し、低温下の耐クラック性能も低下する。
　比較例３の空気入りタイヤは、インナーライナー用ゴム組成物のカーボンブラックの配合量が２５質量部未満であるので、操縦安定性が低下する。
　比較例４の空気入りタイヤは、インナーライナー用ゴム組成物のカーボンブラックの配合量が７５質量部を超え、－４５℃の動的貯蔵弾性率が６００ＭＰａを超えるので、低温下の耐クラック性能が低下する。
　比較例５の空気入りタイヤは、インナーライナー用ゴム組成物のハロゲン化ブチルの含有量が５０質量％未満であるので、ゴム硬度が低下し操縦安定性が低下する。また耐空気透過性が不足する。
　比較例６の空気入りタイヤは、インナーライナー用ゴム組成物にタルクを配合したので、－４５℃における動的貯蔵弾性率が６００ＭＰａを超え、低温下の耐クラック性能が低下する。 In the pneumatic tire of Comparative Example 1, the blending amount of zinc oxide in the rubber composition for the inner liner exceeds 1.8 parts by mass, and the dynamic storage elastic modulus at −45 ° C. exceeds 600 MPa. However, the crack resistance performance at low temperatures also decreases.
In the pneumatic tire of Comparative Example 2, the compounding amount of the resin of the rubber composition for the inner liner exceeds 13 parts by mass, and the dynamic storage elastic modulus at −45 ° C. exceeds 600 MPa. Lower crack resistance performance is also reduced.
In the pneumatic tire of Comparative Example 3, since the blending amount of carbon black in the rubber composition for the inner liner is less than 25 parts by mass, the steering stability is lowered.
In the pneumatic tire of Comparative Example 4, the amount of carbon black in the rubber composition for the inner liner exceeds 75 parts by mass, and the dynamic storage elastic modulus at −45 ° C. exceeds 600 MPa. descend.
In the pneumatic tire of Comparative Example 5, since the content of butyl halide in the rubber composition for the inner liner is less than 50% by mass, the rubber hardness is lowered and the steering stability is lowered. Moreover, the air permeation resistance is insufficient.
In the pneumatic tire of Comparative Example 6, since talc was blended with the rubber composition for the inner liner, the dynamic storage elastic modulus at −45 ° C. exceeded 600 MPa, and the crack resistance performance at low temperatures was lowered.
１　　トレッド部
２　　サイド部
３　　ビード部
４　　カーカス層
７　　タイゴム
８　　インナーライナー 1 Tread part 2 Side part 3 Bead part 4 Carcass layer 7 Tie rubber 8 Inner liner

Claims (3)

  1. 　インナーライナーおよびタイゴムを有する空気入りタイヤであって、前記インナーライナーを構成するインナーライナー用ゴム組成物が、ハロゲン化ブチルゴムを５０～１００質量部含むジエン系ゴム１００質量部に、窒素吸着比表面積が２５～９５ｍ2／ｇであるカーボンブラックを２５～７５質量部、樹脂を１～１３質量部、酸化亜鉛を０．１～１．８質量部配合してなり、その－４５℃における動的貯蔵弾性率が６００ＭＰａ以下であることを特徴とする空気入りタイヤ。 A pneumatic tire having an inner liner and a tie rubber, wherein the rubber composition for an inner liner constituting the inner liner has a nitrogen adsorption specific surface area of 100 parts by mass of a diene rubber containing 50 to 100 parts by mass of a halogenated butyl rubber. 25-75 parts by mass of carbon black of 25-95 m 2 / g, 1-13 parts by mass of resin, and 0.1-1.8 parts by mass of zinc oxide are blended and dynamically stored at −45 ° C. A pneumatic tire having an elastic modulus of 600 MPa or less.
  2. 　前記インナーライナー用ゴム組成物のひずみ率１２０％、周波数６．６７Ｈｚの定歪疲労試験における破壊繰り返し変形回数が８００，０００回以上であることを特徴とする請求項１に記載の空気入りタイヤ。 2. The pneumatic tire according to claim 1, wherein the number of repeated fracture deformations in the constant strain fatigue test at a strain rate of 120% and a frequency of 6.67 Hz of the rubber composition for an inner liner is 800,000 times or more.
  3. 　前記インナーライナー用ゴム組成物のゴム硬度ＨＳILに対する、前記タイゴムを構成するタイゴム用ゴム組成物のゴム硬度ＨＳTの比ＨＳT／ＨＳILが１．１以上であることを特徴とする請求項１または２に記載の空気入りタイヤ。 The ratio HS T / HS IL of the rubber hardness HS T of the rubber composition for tie rubber constituting the tie rubber to the rubber hardness HS IL of the rubber composition for the inner liner is 1.1 or more. The pneumatic tire according to 1 or 2.
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